Dyes of the quinophthalone series



DYES OF THE QUINOPHTHALONE saunas Frithjof Zwilgmeyer, Wilmington, Del., assignor to E. I. du Pont de Nemours and Company, Wilmington, Del., a corporation of Delaware No Drawing. Application February 23, 1956 Serial No. 567,091

7 Claims. (Cl. 260-288) This invention relates to novel compounds of the quinophthalone series.

It is an object of this invention to provide novel disperse dyes which are useful for dyeing polyethylene terephthalate fiber, nylon, cellulose acetate and similar hydrophobic fibers. A particular object of this invention is to provide dyes which shall produce upon the mentioned fibers yellow dyeings of good light fastness, good sublimation resistance and good build-up properties. Additional objects and achievements of this invention will appear as the description proceeds.

According to this invention, the above objects are satisfied by a group of novel compounds which may be designated broadly as quinophthalones possessing nitrogenous substituents in the phenyl ring of the phthalone radical. More particularly, my novel compounds may be defined by the general formula oH/ii; X z

wherein X designates nitro or amino, while Y and Z may designate hydrogen, chlorine, bromine or methyl. Inasmuch as tautomeric rearrangements of this formula are theoretically admissible, for instance, the structure E X RC/ wherein R stands for the hydroxyquinolyl radical and the indicated substitution derivatives thereof, it will be understood that all formulas in this case are to be construed in a liberal sense, to include tautomeric rearrangements of the same formulas.

My novel compounds may be synthesized by condensing a 3-hydroxy-quinaldine having substituents Y and Z as above defined in the Bz nucleus with a nitrophthalie acid. The nitro group in the latter may be in position 3 or 4, the two carboxy groups being in positions 1 and 2. The quinaldine compound may possess a carboxy group in the 4 position, inasmuch as such a group is generally eliminated during the course of the reaction, being replaced by hydrogen. The initial quinaldine material may therefore be defined by the general formula "ice wherein Q stands for H or COOH, while Y and Z stand for hydrogen, halogen or methyl. The substituents Y and Z may be located in any of the four positions of the Bz ring.

Synthesis is generally elfected by heating the two components in an inert organic solvent at a temperature of to 250 C. As inert solvent may be employed any common organic liquid which is stable at the reaction temperature, for instance o-dichlorobenzene, trichlorobenzene or nitrobenzene.

The above synthesis produces the novel nitro compounds of this invention. Reduction of the latter, which can be readily achieved for instance by the aid of iron and acetic acid, produces the corresponding amino compounds.

Without limiting this invention, the following examples are given to illustrate my preferred mode of operation. Parts mentioned are by weight.

Example 1.-4-nitr0-3-hydroxyquinophthal0ne 211 parts of 3-nitrophthalic acid, 203 parts of 2- methyl-3-hydroxyquinoline-4-carboxylic acid, and 2600 parts of o-dichlor'obenzene are mixed and heated at to C. for 18 hours. The mixture is allowed to cool to room temperature and is then agitated with 7000 parts of 3% sodium hydroxide solution (in water) and 30 parts of activated charcoal. The slurry is filtered, and the o-dichlorobenzene layer is separated from the aqueous layer. Concentrated aqueous hydrochloric acid is added to the aqueous phase to adjust the alkalinity to pH 8, thereby precipitating 4-nitro-3hydroxyquinophthalone from the aqueous solution of its sodium salt. The yellow dye is filtered from this mass, washed saltfree with water, and dried at 100 C. It dyes cellulose acetate, nylon and Dacron polyester fibers in yellow shades from an aqueous, disperse dye bath, exhibiting outstanding fastness on these fibers.

If in lieu of 203 part of 2-methyl-3-hydroxyquinoline- 4-carboxylic acid above, 159 parts of 2-methyl-3-hydroxyquinoline are used, the identical product is obtained.

5-nitro-3'-hydroxyquinophthalone is prepared by substituting 232 parts of 4-nitrophthalic acid for the 3-nitrophthalic acid in Example 1. The dyeing properties of the 5-nitro derivative are similar to those of 4-nitro-3- hydroxyquinophthalone.

Example 3.4-amino-3'-hydroxyquin0phthalone A mixture of 560 parts of ethanol, 525 parts of glacial acetic acid, and 170 parts of powdered iron are mixed and heated to 80 C. The heat is shut oil, and 150 parts of 4-nitro-3-hydroxyquinophthalone are added at such a rate that the heat of reaction stabilizes the temperature of the mixture at 80 C. After all of the 4-nitro-3'-hydroxyquinophthalone has been added, stirring is continued at 80 C. for 16 hours to complete the reduction. The mixture is drowned into a solution of 100 parts of sodium acetate trihydrate in 5000 parts of water, stirred for one hour and filtered. The filter cake containing the 4-amino-3hydroxyquinophthalone is washed with water to remove the iron salts, and dried at 100 C. The dye thus obtained produces bright yellow shades on acetate, nylon, and Dacron polyester fibers.

Example 4.-5-amin0-3'-hydroxyquin0phthal0ne 5-amino-3'-hydroxyquinophthalone is obtained by the substitution of equal parts of 5-nitro-3-hydroxyquinophthalone for 4-nitro-3'-hydroxyquinophthalone in Example 3. Dyeing properties are similar to those of 4- amino-3'-hydroxyquinophthalone.

3' ExampleS '(a) 2.11 parts of 3-nitrophthalic acid, 3.61 parts of 2-methyl-3-hydroxy-6,8-dibrdfnoquinoline 4 carboxylic acid and 2 6 parts (if o dichlotobenzene" are mixed and heated-M165 tot-170 for 18-hours. The n'iixthre is allowed to cool below 100'C. and then is agitated with sutficient 30% aqueous sodium hydroxide to render the medium alkaline to Brilliant Yenow paper. The alkaline mass is" then filtered, and the filter cake is washed alkali-free with hot Water followed by Washing with petroleiim ether (petroleum-hydrocarbon, boiling range 45 to 60 C.). 3-hydroxyquinophtl1alone, dyes Dacron polyester fiber in yellow shades being somewhat redder tlian'the dyeings obtained fi'ornthe product of Example 1.

(b) When the 2-rne'thyl=3-liydrmy=6,8-dibromoquino 1ine-4-carbcx l-ieacid in part (a) of this example is replaced by an equivalent amount respectively of (i1) 2- methyl 3 liydroxy fi-bromo'c'iuinoline-4=carboxylic acid, (6) 2 methyid'hydroxwfi,s-dichloroquinolineAcarbon ylic acid or (d) 2,8-dim'ethyl-3-hydroXy-7-chloroquinm line-4-carb0xylic acid yellow disperse dyes of similar properties are obtained.

(c) When the 3 nitr'oplitlialic acid in parts (a) and (b) of this example is'replaced with the same amount of 4-nitrophth'alie acid, the corresponding derivatives of 5-nitro-3'-hydroxyquinophthalone are obtained. The 4 and S-nitro isomers p'o'ssess' similar shade and dyeing properties. I

It will be clear from the above discussion that my invention provides novel compounds which are of great interest in connection with the dyeing of hydrophobic fibers. My novel dyes have good buildup on nylon, cellulose acetate and Dacron polyester fibers, and dye these fibers in desirable yellow shades. All of the new compounds exhibit good toexcellent light sublimation, and w'ash-fastne'ss on these fibers. The 45 and 5-nitro derivatives are particularly otitstanding as light-fast yet low dyes" for Dacron polyester fiber.

It will be further understood, that the details of the above examples may be varied Within the skill of those engaged in this" art.

I claim as my invention; 1. A compound of the formula and its tautomers, wherein R represents a hydroxyquinolyl radical of the group consisting of 3-hydroxy-2 quinolyl afidits B2 chlorine, bromine-and methyl derivatives, while X designates a substituent of the group consisting of nitro and amino."

2. 4-nitro-3'hydroxyquinophthalone.

3. 5-nitro-3'-hydroxyquinophthalone.

4. 4*amino-3f hydroityquinophthalone.

5. 5-amino-3'-hydroxyquinophthalone.

6. A process of: producing a coloring matter of the quinophthalone" series, which comprises heating one molecule of nitrophthalic anhydride Withsubstantially one molecule of a Z-methyl-B-hydroxyquinoline-4 carboxylic acid in an inertorganic' solvent at a temperature of 160 to 250 C., andrecoveringthe reaction product.

7. A process. as in claimi.6,.fcllowed by reduction of the recoveredzcompound to" c onvert its nitro group into an amino group.

References Cited in the file of this patent UNITED STATES PATENTS 1,963,374 ogilvie June 19, 1934 2,006,022 Kmaaein June 5, 1935 2,121,320 Kranzlein June 21, 1938 OTHER REFERENCES Zalukajevs: Lat vijqs PSR Zintanu Akad. Vestis, 1953, No. 11 (Whole No. pages 11 1-118 as cited in Chem. Abs. vol. 49, 1955, 7568.

Venkataraman: The Chem. of Synth Dyes, 2 volumes, Academic Press, 1952, pages 323328, 457-458 and 1198-99. 

1. A COMPOUND OF THE FORMULA
 6. A PROCESS OF PRODUCING A COLORING MATTER OF THE QUINOPHTHALONE SERIES, WHICH COMPRISES HEATING ONE MOLECULE OF NITROPHTHALIC ANHYDRIDE WITH SUBSTANTIALLY ONE MOLECULE OF A 2-METHYL-3HYDROXYQUINCLINE-4-CARBOXYLIC ACID IN AN INERT ORGANIC SOLVENT AT A TEMPERATURE OF 160* TO 250*C. AND RECOVERING THE REACTION PRODUCT. 